CN103717703B - Nitride red fluorophor - Google Patents

Nitride red fluorophor Download PDF

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Publication number
CN103717703B
CN103717703B CN201280037886.6A CN201280037886A CN103717703B CN 103717703 B CN103717703 B CN 103717703B CN 201280037886 A CN201280037886 A CN 201280037886A CN 103717703 B CN103717703 B CN 103717703B
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fluorescencer composition
range
light
fluorescencer
composition
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CN103717703A (en
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H.A.塞贝尔二世
B.T.科林斯
D.T.埃默森
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Kerui Led Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/484—Connecting portions
    • H01L2224/48463—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond
    • H01L2224/48465—Connecting portions the connecting portion on the bonding area of the semiconductor or solid-state body being a ball bond the other connecting portion not on the bonding area being a wedge bond, i.e. ball-to-wedge, regular stitch

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Led Device Packages (AREA)

Abstract

There is provided according to embodiment of the present invention and comprise Ca1‑x‑ ySrxEuyAlSiN3Fluorescencer composition, wherein in the range of 0.50 0.99 and y is less than 0.013 for x.Also provide for comprising Ca according to embodiment of the present invention1‑x‑ySrxEuyAlSiN3Fluorescencer composition, wherein in the range of 0.70 0.99 and y is in the range of 0.001 0.025 for x.Additionally provide the method manufacturing fluorophor and the light-emitting device comprising the fluorescencer composition according to one embodiment of the invention.

Description

Nitride red fluorophor
Invention field
The present invention relates to fluorescencer composition and the light-emitting device comprising fluorescencer composition.
Background
Light emitting diode (" LED ") is the known solid-state lighting device that can produce light.LED generally includes can be at such as sapphire, silicon, carborundum, gallium nitride or the quasiconductor of GaAs base material or multiple semiconductor layers of non-semiconductor base material Epitaxial growth.One or more semiconductor p-n junctions is formed in these epitaxial layers.When applying enough voltage at p-n junction two ends, flow to p-n junction in the electronics in n-type semiconductor layer and the hole in p-type semiconductor layer.Along with electronics and hole flow to each other, some electronics " will collide " with hole and be combined.Compound tense occurs every time, and the photon of light is launched, and LED is exactly so to produce light.The Wavelength distribution of the light produced by LED generally depends on the structure of the thin epitaxial layer in " active region " (that is, the region that electronics and hole are combined wherein) of used semi-conducting material and component devices.
LED is generally of closely narrow Wavelength distribution centered by " peak value " wavelength (that is, as reached single wavelength during its maximum by the radiometric quantities emission spectrum of LED that photoelectric detector detects).Such as, the spectral power distribution of typical LED can have the full duration of e.g., from about 10-30nm, and wherein this width measures (referred to as full width at half maximum (full width half maximum) or " FWHM " is wide) under the half of maximal illumination.Therefore, LED usually through its " peak value " wavelength or " leads " wavelength by it and identifies.The dominant wavelength of LED be perceived by human eye with the light sent by LED, there is the monochromatic wavelength of identical apparent colour.Therefore, dominant wavelength is different from peak wavelength, because dominant wavelength considers the human eye sensitivity to the light of different wave length.
Because most of LED are the monochromaters seeming to launch the light with solid color, include that the LED launching multiple LED of the light of different colours is to provide the solid luminous device producing white light so having used.In these devices, by the wanted intensity of light combination producing and/or the white light of color of the different colours by single LED chip transmitting.Such as, according to red, green and the relative intensity in blue led source, by while excitation-emission HONGGUANG, green glow and the LED of blue light, gained combination light can present white or close to white.
White light also can generate by surrounding monochromatic LED with luminescent material, and this luminescent material will be converted into the light of other colors by some in the light of LED emission.White can be generated by what monochromatic LED was launched through the light of material for transformation of wave length and the combination of the light of the different colours launched by material for transformation of wave length or connect subalbous light.Such as, single blue-light-emitting LED chip (such as, being made up of InGaN and/or gallium nitride) can (it has chemical formula Y with the yttrium-aluminium-garnet of yellow fluorophor, polymer or dyestuff such as cerium dopping3-xCexAl5O12, and commonly referred to YAG:Ce) be applied in combination, it is by being changed downwards (down convert) by the wavelength of some blue lights of LED emission, by blue light color yellowing.The blue led being made up of InGaN shows out high efficiency (such as, the external quantum efficiency of up to 60%).In blue led/yellow fluorophor lamp, blue LED die produces the transmitting of the dominant wavelength with about 450-465 nanometer, and this fluorophor responds this blue emission and produces the yellow fluorescence of the peak wavelength with about 545-565 nanometer.Some blue lights are through fluorophor (and/or fluorophor particle) in the case of conversion downwards, and considerable fraction of light is absorbed by fluorophor, and this fluorophor is excited and launches gold-tinted (that is, blue light is changed into downwards gold-tinted).It is white that blue light and the combination of gold-tinted can present to observer.This light generally perceived as cool white.In other method, the light from purple or ultra-violet light-emitting LED can be by surrounding LED with multicolor fluorescence body or dyestuff and be converted into white light.In both cases, it is possible to add red-emitting phosphor particle (such as, based on (Ca1-x-ySrxEuy)AlSiN3Fluorophor), to improve the colour developing character of light, i.e. make light appear more " warm ", particularly when monochromatic LED launches blue light or ultraviolet light.
As it has been described above, fluorophor is the luminescent material of a kind of Known Species." fluorophor " can refer to absorb light under a kind of wavelength of visible spectrum and launch any material of light at different wavelengths again, and with absorb and launch again between postpone unrelated and unrelated with involved wavelength.Therefore, term " fluorophor " can be sometimes referred to as fluorescence and/or phosphorescent material in order to referring in this article.Generally, fluorophor can absorb and has the light of first wave length and launch the light with the second wave length being different from first wave length again.Such as, " conversion downwards " fluorophor can absorb and has the light of shorter wavelength and launch the light with longer wavelength again.
LED is for such as including in the extensive application that the backlight of liquid crystal display, signal lights, automobile headlamp, flash lamp, dedicated illumination are applied and even serving as the conventional incandescent in generally illumination and illumination applications and/or the substitute of fluorescent illumination.In many in such applications, it may be desirable to provide produce the light source of the light with special properties.
General introduction
Some embodiments according to the present invention provide and comprise Ca1-x-ySrxEuyAlSiN3Fluorescencer composition, wherein in the range of 0.50-0.99 and y is less than 0.013 for x.Additionally provide according to embodiment of the present invention and comprise Ca1-x-ySrxEuyAlSiN3Fluorescencer composition, wherein in the range of 0.70-0.99 and y is in the range of 0.001-0.025 for x.In some embodiments of the present invention, in described fluorescencer composition the ratio of Sr Yu Eu in the range of 25-300.In some embodiments of the present invention, described fluorescencer composition exists in granular form and the particle of at least 95% is elongated.In some embodiments of the present invention, described fluorescencer composition exists as the particle of the particle mean size having in 4 μm-20 μ m.
In some embodiments of the present invention, described fluorescencer composition comprises the nitrogen-oxygen-silicon aluminum (silicon of at least 1% weight Aluminum oxynitride), such as Si2Al4O4N4.In some embodiments, described fluorescencer composition exists as monocrystalline.
In some embodiments of the present invention, light under described fluorescencer composition absorbs wavelength in the range of 350-530nm and the crest frequency under the wavelength in the range of being transmitted in 620-660nm.
In some embodiments of the present invention, fluorescencer composition comprises Ca1-x-ySrxEuyAlSiN3Fluorophor particle, wherein x < 1 and y < 1, and described Ca1-x-ySrxEuyAlSiN3At least some in fluorophor particle is elongated.In some embodiments, in the range of 0.5-0.99 and y is in the range of 0.001-0.025 for x.In some embodiments, 50% or more described fluorophor particle is elongated, in some embodiments, and 75% or more described Ca1-x-ySrxEuyAlSiN3Fluorophor particle is elongated, and in some embodiments, 95% or more described Ca1-x-ySrxEuyAlSiN3Fluorophor particle is elongated.
Additionally providing light-emitting device according to embodiment of the present invention, it includes solid state light emitter；With the fluorescencer composition according to one embodiment of the invention.In some embodiments of the present invention, described LED emission has the warm white of the correlated color temperature between about 2700K-5400K.In some embodiments, described light-emitting device has the CRI value more than 90.In some embodiments, described light-emitting device also includes green and/or yellow fluorophor.
The method forming fluorescencer composition is additionally provided according to embodiment of the present invention.In some embodiments, described method include the nitride of calcium mixture, strontium, aluminum and silicon and europium source component (europium source composition) to form precursor mixture, in fire-clay crucible exist form gas (forming gas) in the case of described precursor mixture is heated to the temperature of 1500-1800 DEG C to generate the fluorescencer composition according to one embodiment of the invention.
In some embodiments of the present invention, described precursor mixture heats in the case of being substantially not present water and oxygen.In some embodiments of the present invention, described fire-clay crucible is the most inert in the case of there is described formation admixture of gas.In some embodiments, described formation gas-dynamic described fire-clay crucible is flow through.In some embodiments, described precursor heats at least 0.5 hour at the first temperature, is heated to the second temperature and lasts at least 0.5 hour and be subsequently heated to the 3rd temperature and last at least 0.5 hour.In certain embodiments, described first temperature is 800 DEG C, and described second temperature is 1200 DEG C and described 3rd temperature is 1800 DEG C.
Accompanying drawing is sketched
Fig. 1 is the top view that can be used for being formed the equipment of the fluorescencer composition according to one embodiment of the invention.
Fig. 2 shows the equipment that can be used for forming the fluorescencer composition according to one embodiment of the invention.
Fig. 3 shows and can be used for formation according to the formation gas stream in the equipment of the fluorescencer composition of one embodiment of the invention.
Fig. 4 shows the change in terms of relative luminance of the fluorescencer composition of some embodiments according to the present invention.
Fig. 5 shows the change in terms of relative gamut of the fluorescencer composition of some embodiments according to the present invention.
Fig. 6 provides and represents for relative color from the point of view of the fluorescencer composition according to some embodiments of the present invention and relative luminance with the three-dimensional curve diagram of the change of the ratio of Sr Yu Eu.There is provided arrow to guide eyes in third dimension in shadow region.
Fig. 7 A provides for relative color from the point of view of the fluorescencer composition according to some embodiments of the present invention and relative luminance with the three-dimensional curve diagram of the change of Sr concentration.There is provided arrow to guide eyes in third dimension in shadow region.
Fig. 7 B provides for relative color from the point of view of the fluorescencer composition according to some embodiments of the present invention and relative luminance with the three-dimensional curve diagram of the change of Eu concentration.There is provided arrow to guide eyes in third dimension in shadow region.
Fig. 8 A-8D is the various views of the solid luminous device according to embodiment of the present invention.
Fig. 9 A-9E is the cross-sectional view showing and can be used for being applied to fluorescencer composition the manufacturing step of LED chip wafer according to embodiment of the present invention.
The detailed description of invention embodiment
It is described more fully hereinafter with the present invention, shown in the drawings of embodiment of the present invention referring now to accompanying drawing.But, the present invention should be considered limited to embodiment set forth herein.On the contrary, it is provided that these embodiments will make the disclosure more thoroughly and completely and those skilled in the art will be given full expression to the scope of the present invention.In the accompanying drawings, for clarity, the thickness in layer and region it is exaggerated.Identical symbol represents identical element in the whole text.Terms used herein "and/or" includes any and all combination listd of one or more association.
Terms used herein is simply for the purpose of description particular, and is not used to limit the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singulative " " and " being somebody's turn to do " also in order to include plural form.Should also be appreciated that, when using in this manual, term " comprises " and/or " including " and derivative thereof specify to exist described in feature, operation, element and/or assembly, but be not precluded from existing or adding other features one or more, operation, element, assembly and/or their group.
Should be appreciated that, when the element of such as layer, region or base material is referred to as at " on another element " or extends to " on another element ", it can be directly on this another element or extend directly on this another element or also can there is insertion element.On the contrary, when element is referred to as " directly on another element " or " extending directly on another element ", the most there is not insertion element.Be also to be understood that it may be coupled directly to or be coupled to this another element, or can there is insertion element when element is referred to as " being connected to " or " being coupled to " another element.On the contrary, when element is referred to as " being directly connected to another element " or " extending directly into another element ", connection insertion element is not the most deposited.
It is to be understood that, although first, second term such as grade can be used for describing various element, assembly, region and/or layer in this article, but these elements, assembly, region and/or layer should not be limited by these terms.These terms are only used for distinguishing an element, assembly, region or layer and another element, assembly, region or layer.Therefore, the first element, assembly, region or the layer being discussed herein below can be referred to as the second element, assembly, region or layer without departing from the teachings of the present invention.
Additionally, such as " under " or " bottom " and " on " or the relative terms at " top " can be in this article in order to describe the relation of an element as shown in the figure and another element.Should be appreciated that in addition to the direction painted in the drawings, relative terms is also intended to contain the different directions of device.Such as, if the device in figure is overturn, then the element being described as on the D score side of other elements will be orientated in other elements " on " on side.Therefore, according to the specific direction of figure, exemplary term " under " can include " under " and " on " both direction.
Unless specified otherwise herein, all terms (including scientific and technical terminology) the most used herein all have the implication identical with the implication that those skilled in the art in the invention are generally understood.It should also be understood that, unless the most so specified, the most such as in normally used dictionary, the term of those terms of regulation should be construed to have the implication consistent with they implications in the context of the application and association area, and should not explain to idealize or to cross the meaning of form-separating.
The all patents and patent applicationss mentioned in this article are incorporated herein in the most in full.In the case of term or range conflicts, it is as the criterion with the application.
Terms used herein " solid luminous device " can include light emitting diode, laser diode and/or other semiconductor devices, and it includes that one or more semiconductor layer, described semiconductor layer can comprise silicon, carborundum, gallium nitride and/or other semi-conducting materials；Optional base material, described base material can comprise sapphire, silicon, carborundum；And/or other microelectronic substrates；With one or more contact layers, described contact layer can comprise metal and/or other conductive materials.The design of solid luminous device and be fabricated to well known to those skilled in the art.Statement used herein " light-emitting device " is unrestricted, and difference is that it is the device that can launch light.
Solid luminous device according to embodiment of the present invention may be included on carborundum or gallium nitride base material manufacture based on III-V nitride (such as, gallium nitride) LED or laser instrument, such as by Durham, the device that the Cree of N.C., Inc. produce and sell.This kind of LED and/or laser instrument can (or can not) be configured as being operable so that at so-called " upside-down mounting (flip Chip) " side is upwardly through base material generation light emission.Solid luminous device according to embodiment of the present invention includes the negative electrode contact having on the side of chip and the vertical means of the anode contact on the opposition side of described chip and two of which contact device on the same side of device.nullSome embodiments of the present invention can use such as solid luminous device described in following patent、Device is set with、Fixing equipment (fixture)、Luminescent material/element、Power supply supplies、Control element and/or method: United States Patent (USP) 7,564,No. 180、United States Patent (USP) 7,456,No. 499、United States Patent (USP) 7,213,No. 940、United States Patent (USP) 7,095,No. 056、United States Patent (USP) 6,958,No. 497、United States Patent (USP) 6,853,No. 010、United States Patent (USP) 6,791,No. 119、United States Patent (USP) 6,600,No. 175、United States Patent (USP) 6,201,No. 262、United States Patent (USP) 6,187,No. 606、United States Patent (USP) 6,120,No. 600、United States Patent (USP) 5,912,No. 477、United States Patent (USP) 5,739,No. 554、United States Patent (USP) 5,631,No. 190、United States Patent (USP) 5,604,No. 135、United States Patent (USP) 5,523,No. 589、United States Patent (USP) 5,416,No. 342、United States Patent (USP) 5,393,No. 993、United States Patent (USP) 5,359,No. 345、United States Patent (USP) 5,338,No. 944、United States Patent (USP) 5,210,No. 051、United States Patent (USP) 5,027,No. 168、United States Patent (USP) 5,027,No. 168、United States Patent (USP) 4,966,No. 862 and/or United States Patent (USP) 4,918,No. 497 and U.S. Patent Application Publication 2009/0184616、U.S. Patent Application Publication 2009/0080185、U.S. Patent Application Publication 2009/0050908、U.S. Patent Application Publication 2009/0050907、U.S. Patent Application Publication 2008/0308825、U.S. Patent Application Publication 2008/0198112、U.S. Patent Application Publication 2008/0179611、U.S. Patent Application Publication 2008/0173884、U.S. Patent Application Publication 2008/0121921、U.S. Patent Application Publication 2008/0012036、U.S. Patent Application Publication 2007/0253209、U.S. Patent Application Publication 2007/0223219、U.S. Patent Application Publication 2007/0170447、U.S. Patent Application Publication 2007/0158668、U.S. Patent Application Publication 2007/0139923 and/or U.S. Patent Application Publication 2006/0221272.
Provide according to embodiment of the present invention and comprise Ca1-x-ySrxEuyAlSiN3Fluorescencer composition, wherein in the range of 0.50-0.99 and y is less than 0.013 for x.In the particular of the present invention, y is in the range of 0.001-0.013, and in certain embodiments, y is in the range of 0.001-0.012.Additionally provide according to embodiment of the present invention and comprise Ca1-x-ySrxEuyAlSiN3Fluorescencer composition, wherein in the range of 0.70-0.99 and y is in the range of 0.001-0.025 for x.It addition, in some embodiments, x is in the range of 0.71-0.99, and in certain embodiments, x is in the range of 0.70-0.90.In some embodiments of the present invention, in described fluorescencer composition the ratio of Sr Yu Eu in the range of 25-300.
Although described Ca1-x-ySrxEuyAlSiN3The oxygen of minimum can be comprised, but the most there is not the oxygen that be enough to affect the crystal structure formed by nitride.Therefore, described Ca1-x-ySrxEuyAlSiN3It it not nitrogen oxides fluorophor.Those skilled in the art recognizes, the amount that there is not restriction oxygen makes said composition classify as nitrogen oxides rather than the obvious line of nitride or exact boundary, but in general, in nitride phosphor, the oxygen that the amount of only existing is considerably less, such as, compared with the amount of nitrogen, there is the oxygen less than (5%) 5 percent.What described fluorescencer composition can comprise more than one type has formula Ca1-x-ySrxEuyAlSiN3Fluorophor, and/or can comprise and described Ca1-x-ySrxEuyAlSiN3Other fluorophor in combination or other phosphorescent compositionss (in both another compositionss in same fluorescencer composition or in device as herein described).
Although described Ca1-x-ySrxEuyAlSiN3It not nitrogen oxides fluorophor, but in some embodiments of the present invention, described Ca1-x-ySrxEuyAlSiN3Fluorescencer composition comprises the silicon aluminum oxynitride phase of the separation of at least 1 weight %.In some embodiments, described silicon aluminum oxynitride comprises Si mutually2Al4O4N4。
Described fluorophor can exist in any suitable form, and described form includes but not limited to particle, block or phosphor structures known to other.In some embodiments, described fluorescencer composition exists as the particle of the particle mean size having in about 2.0 μm-25 μ m.Described mixture can be pulverized in a usual manner to use as may want to or be required.The size of the particle pulverized depends on finally applying and in most of the cases can being selected by end user.Described particle can also any suitable shape obtain, and described shape includes elongated shape, spherical and/or hemispherical.In some embodiments, in described fluorescencer composition, 50%, 75% or 95% or more particle is elongated.In some embodiments, in described fluorescencer composition, 50%, 75% or 95% or more particle is spherical or substantially spherical.Having been found that in some embodiments, along with calcium concentration reduces, particle will become more elongated.
In some embodiments of the present invention, fluorescencer composition comprises Ca1-x-ySrxEuyAlSiN3Fluorophor particle, wherein x < 1 and y < 1, and Ca described at least some1-x-ySrxEuyAlSiN3Fluorophor particle is elongated.In some embodiments, in the range of 0.5-0.99 and y is in the range of 0.001-0.025 for x.In some embodiments, 50% or more described Ca1-x-ySrxEuyAlSiN3Fluorophor particle is elongated, in some embodiments, and 75% or more described Ca1-x-ySrxEuyAlSiN3Fluorophor particle is elongated, and in some embodiments, 95% or more described Ca1-x-ySrxEuyAlSiN3Fluorophor particle is elongated.Also the post-treatment of described fluorophor can be carried out, such as at entitled nitride red fluorophor (Red Nitride Phosphors) U.S. Patent application 12/466 that 15 days Mays in 2009 submit to, No. 782 and the U.S. Patent application 13/152 of submission on June 3rd, 2011, method described in No. 863, entire contents of these patents is incorporated herein in by way of reference.
The method also providing for forming fluorescencer composition according to embodiment of the present invention.In some embodiments, described method include the nitride of calcium mixture, strontium, aluminum and silicon and europium source component to form precursor mixture, and subsequently exist form gas in the case of heat described precursor mixture and be less than described precursor composition or described fluorophor by decomposition or the temperature of the temperature with crucible reaction to being enough to generate described fluorophor.Described reaction carries out being enough to generate the time of fluorescencer composition, described fluorescencer composition can be by the blueness of spectrum and ultraviolet region (i.e., between about 430-480nm) in photon change into downwards the photon in the longer wavelength region (that is, between about 530-750nm) of visible spectrum.It would be recognized by those skilled in the art that in descriptive manner rather than use color boundaries in the visible spectrum with restrictive, sense.
In some embodiments, this heating of described precursor mixture is carried out in the case of being substantially not present water and oxygen.In some embodiments, described precursor mixture is heated to the temperature in the range of 1500 DEG C-1800 DEG C.
Phrase used herein " europium source component " refers to the component that will generate the europium as the activator cation in the lattice of fluorophor under the reaction condition stated in this article.Such as, in some embodiments, europium is described europium source component.
Terms used herein " formation gas " refers to the mixture of nitrogen and hydrogen.In some embodiments, form gas and there is of a relatively high nitrogen content.Such as, in some cases, form the nitrogen under the concentration in the range of gas is included in 90-95 volume % and described hydrogen exists with the concentration in the range of 5%-10%.
In some embodiments of the present invention, described mixture at atmosheric pressure or is heated near atmospheric pressure.Terms used herein " at atmosheric pressure or near atmospheric pressure " refers to need not the pressure of high pressure equipment.
In some embodiments, described precursor mixture is heated in fire-clay crucible.In some embodiments of the present invention, described fire-clay crucible is the most inert in the case of there is described formation admixture of gas.Such as, in some embodiments, described fire-clay crucible comprises molybdenum.In inappropriate crucible material, synthesize fluorophor can reduce the optical property of fluorophor.Described degradation is generally caused by certain reaction between crucible material and reactant.Such as, when using alumina crucible in the reaction being similar to method described herein, the oxygen from crucible is prone to and is attached in gained fluorophor powder, then making gained fluorophor powder have bad luminescent quality.Such as, in some embodiments, it has been determined that the crucible of tungsten (W) and molybdenum (Mo) is favourable.Tungsten and molybdenum are refractory metal, and they can tolerate high temperature and for inertia under appropriate atmosphere.
In some embodiments of the present invention, the multiple steps of described heating steps (burning) point are carried out at different temperatures, have suitable even change between each temperature.In some embodiments of the present invention, described precursor mixture heats at least 0.5 hour at the first temperature, is heated to the second temperature and lasts at least 0.5 hour and be subsequently heated to the 3rd temperature and last at least 0.5 hour.In some embodiments, described temperature between heating steps with 350 DEG C/h of even changes.In some embodiments, described first temperature is 800 DEG C, and described second temperature is 1200 DEG C and described 3rd temperature is 1800 DEG C.
Any suitable method forming described fluorescencer composition can be used.However, it is possible to use certain methods see in the U.S. Patent application 12/271,945 that on November 17th, 2008 submits to, the content of this patent application is incorporated herein in full by way of reference.In some embodiments, described fluorescencer composition is formed by the following method.Fig. 1 is the top view of the relatively large alumina crucible being designated broadly at 10.In some embodiments of the present invention, by the nitride (Ca of calcium3N2), the nitride (Sr of strontium2N), the nitride (AlN) of aluminum and the nitride (Si of silicon3N4) mix in the glove box (not shown) be substantially free of water and oxygen according to target chemical metering with europium.In the tungsten being expressed as circular crucible 11 subsequently powder being loaded on the bottom surface 12 being shelved on big alumina crucible 10 or molybdenum crucible.Gas flow tube 13 puts into the inside of crucible 10 through cylindrical wall 14.
Fig. 2 shows crucible 10 and lid 15 and the exterior section of gas tube 16.Alumina crucible 10 is placed in the batch-type furnace being designated broadly at 17.Alumina crucible 10 is the most required.If stove itself is suitable for containing synthesis atmosphere, the alumina crucible 10 illustrated the most in the accompanying drawings can be optional.Pipe 16 is generally formed by ceramic material, and it is selected to not affected by formation gas or any compositions or fluorophor itself for forming fluorophor equally.It is used for batch-type furnace 17 subsequently using previously described thermal cycle to carry out heating material.Fig. 3 is the cross-sectional view of the alumina crucible 10 showing cylindrical wall 14 and lid 15.Earthenware 16,13 extends through wall 14 and arrives the inside of alumina crucible 10 and arrow diagrammatically illustrates the formation gas flowing through tungsten or molybdenum crucible 11.Other structures including that wherein alumina crucible more closely assembles around tungsten or molybdenum crucible 11 can be used.
As shown in FIG. 3, crucible inserts the earthenware in bigger alumina crucible and by forming gas (such as, 95% N by use2/5% H2) kinetic current surround.Batch-type furnace is heated to 800 DEG C and lasts 1 hour, be subsequently heated to 1200 DEG C and last 1 hour, and be subsequently heated to 1800 DEG C and last 2 hours.Temperature ramp rate is 350 DEG C/h.Described method can generate the Ca according to the present invention1-x-ySrxEuyAlSiN3Fluorescencer composition, it also comprises the free phase of the silicon aluminum oxynitride containing at least 1%.
Under these conditions, described fluorophor can under environment (that is, air) pressure or near synthesis, therefore provide significant technological advantage for high pressure technique and the needs of equipment by avoiding.Think and be substantially not present oxygen and water (but being not completely absent) allows formation silicon aluminum oxynitride phase.Have surprisingly discovered that the fluorophor comprising this phase can have desirable optical property.
Also provide for comprising the light-emitting device of fluorescencer composition as herein described according to embodiment of the present invention.Thus, in some embodiments, light-emitting device includes solid state light emitter and the fluorescencer composition according to one embodiment of the invention.
Fig. 4 and Fig. 5 provides the curve chart that relative luminance and relative color become for according to the fluorophor of embodiment of the present invention with europium and strontium concentration.It has been surprisingly found that for given Sr concentration, along with europium concentration reduces, brightness and gamut increase.It addition, for given Eu concentration, along with Sr concentration increases, brightness and gamut increase.Fig. 6 shows the change with the ratio of Sr Yu Eu of relative luminance and relative color.Along with the ratio of Sr Yu Eu increases, relative luminance also increases.Fig. 7 A shows the change with Sr concentration of relative luminance and relative color.Fig. 7 B shows the change with Eu concentration of relative luminance and relative color.This entitled " method determining and preparing nitride red fluorescencer composition " (Methods submitted on June 3rd, 2011 Of Determining and Making Red Nitride Phosphor Compositions) U.S. Patent application 13/153,155 in discuss, the content of this patent application is incorporated herein in full by way of reference.
Describing solid luminous device 30 referring now to Fig. 8 A-8D, it comprises the fluorescencer composition according to embodiment of the present invention.Solid luminous device 30 includes the LED of packaging.Specifically, Fig. 8 A is the perspective view of the solid luminous device 30 not having its lens.Fig. 8 B is the perspective view of the device 30 observed from opposite side.Fig. 8 C is the side view of the device 30 with the lens covering LED chip.Fig. 8 D is the upward view of device 30.
As shown in fig. 8 a, solid luminous device 30 includes the base material/time adhesion base station (submount) 32 of mounted thereon single led chip or " chip (die) " 34.Secondary adhesion base station 32 can be formed by many different materials of such as aluminium oxide, aluminium nitride, organic insulator, printed circuit board (PCB) (PCB), sapphire or silicon.LED 34 can have the semiconductor layer that differently arranged many is different.LED structure and manufacture and operation thereof commonly known in the art and the most only brief discussion.The layer of LED 34 can use the known method manufacture of such as metal organic chemical vapor deposition (MOCVD).LED The floor of 34 can include at least one the active layer/district being clipped between the first relative doped epitaxial floor and the second doped epitaxial floor, and all of which is sequentially formed on growth base material.Generally, many LED grow to provide the semiconductor crystal wafer of growth on the growth base material of such as sapphire, carborundum, aluminium nitride (AlN) or gallium nitride (GaN) base material, and this wafer may be partitioned into single led chip subsequently, it is arranged on them in packaging to provide the LED of individual packaging.The base material of described growth can retain as a part of the LED of final segmentation, or the base material of described growth can completely or partially be removed.In the embodiment of the base material retaining described growth wherein, can be by its molding and/or texturing to strengthen light extraction.
It is also appreciated that other layer and element also are included in LED 34, described layer includes but not limited to buffering, nucleation with element, contact and current spreading layer and light-extraction layer and element.It is also appreciated that the layer of described phase contra-doping can include multiple layer and sublevel and superlattice structure (super Lattice structure) and intermediate layer.Described active region can such as include single quantum well (SQW), MQW (MQW), double-heterostructure or superstructure.Described active region and doped layer can be by different material system manufactures, described material system such as includes material system based on III-th family nitride, such as GaN, aluminium gallium nitride alloy (AlGaN), InGaN (InGaN) and/or aluminum indium gallium nitride (AlInGaN).In some embodiments, described doped layer is GaN and/or AlGaN layer, and described active region is InGaN layer.
LED 34 can be the ultraviolet of radiation, purple or the blue led launched and have the dominant wavelength in the range of about 380-about 475nm.
LED 34 may be included in the conductive current distribution structure 36 on its end face and can reach at its end face to go between the one or more contacts 38 engaged.Both distribution structure 36 and contact 38 all can be made up of the conductive material of such as Au, Cu, Ni, In, Al, Ag or a combination thereof, conductive oxide and transparent conductive oxide.Electric current distribution structure 36 may be included in the conductive contact finger 37 arranged on LED 34 with pattern, and described fingertip is spaced apart to strengthen electric current from contact 38 to LED The distribution of the end face of 34.In operation, the signal of telecommunication as described below is applied to contact 38 through bonding wire, and this signal of telecommunication spreads in LED 34 through the fingertip 37 of electric current distribution structure 36.Electric current distribution structure is usually used in during wherein end face is the LED of p-type, but it can be used for n-type material.
LED 34 can be coated with the fluorescencer composition 39 according to embodiment of the present invention.It should be understood that fluorescencer composition 39 may be included in any fluorescencer composition discussed in the present invention.
Fluorescencer composition 39 can use many different methods to be coated on LED 34, wherein suitably method is described in U.S. Patent application 11/656, No. 759 and U.S. Patent application 11/899, in No. 790, the title of the two patent application is all wafer scale phosphor coated method and the device (Wafer using described method to manufacture Level Phosphor Coating Method and Devices Fabricated Utilizing Method).Or, fluorescencer composition 39 can use the additive method of such as electrophoretic deposition (EPD) to be coated on LED 34, and wherein suitably method of EPD is described in closed loop electrophoretic deposition (the Close Loop Electrophoretic Deposition of entitled semiconductor device Of Semiconductor Devices) U.S. Patent application 11/473,089 in.Herein with reference to Fig. 9 A-9E, a kind of exemplary methods being applied on LED 34 by fluorescencer composition 39 is described.
Optical element or lens 70 (seeing Fig. 8 C-8D) are formed on LED 34 on the end face 40 of secondary adhesion base station 32, to provide both environmental conservation and/or mechanical protection.Lens 70 can use different forming technique molding, and described technology is such as at entitled light emitting diode package and manufacture method (Light thereof Emitting Diode Package and Method for Fabricating Same) U.S. Patent application 11/982,275 described in method.Lens 70 can have many different shapes, such as hemispherical.Lens 70 can use many different materials, such as polysiloxanes, plastics, epoxy resin or glass.Lens 70 also can texturing to improve light extraction and/or scattering particles.In some embodiments, lens 70 can comprise fluorescencer composition 39, and/or replaces being coated directly onto in LED chip 34 fluorescencer composition 39 and/or outer lens 70 except being coated directly onto in LED chip 34 by fluorescencer composition 39 may be used to fluorescencer composition 39 is retained on the appropriate location on LED 34.
Solid luminous device 30 can include the LED packaging with different size or footprint.In some embodiments, the surface area of LED chip 34 can cover 10% or even 15% of the surface area more than time adhesion base station 32.In some embodiments, the ratio of the diameter D of the width W of LED chip 34 and lens 70 (or width D, for square lens) can be more than 0.5.Such as, in some embodiments, solid luminous device 30 can include having the LED packaging of foursquare adhesion base station 32 of about 3.45mm and have the hemispherical lens of maximum gauge of about 2.55mm.Described LED packaging may be disposed to hold the foursquare LED chip of about 1.4mm.In this embodiment, the surface area of LED chip 34 covers 16% of the surface area more than time adhesion base station 32.
The end face 40 of secondary adhesion base station 32 can have can include chip attachment pad 42 and the pattern conductive parts of the first complete touch pad 44.Second touch pad 46 is also included within the end face 40 of time adhesion base station 32, and wherein LED 34 is installed substantially at the center of attachment pad 42.Attachment pad 42 and the first touch pad 44 and the second touch pad 46 can comprise metal or other conductive materials, such as copper.Copper packing 42,44,46 can be plated on copper crystal seed layer, and this copper crystal seed layer is formed on titanium adhesion layer then.Pad 42,44,46 can use standard photolithography techniques to pattern.The conductive component of these patternings provides and uses known contact method to be electrically connected to LED The conductive path of 34.LED 34 can use known method and material to be installed to attachment pad 42.
Gap 48 (seeing Fig. 8 A) be included in the second touch pad 46 and be down to time adhesion base station 32 surface on attachment pad 42 between.The signal of telecommunication is applied to LED 34 through the second pad 46 and the first pad 44, and wherein the signal of telecommunication on the first pad 44 is passed directly to LED 34 and this signal through attachment pad 42 and pads 46 through bonding wire leads to LED 34 from second.Gap 48 provides the electric insulation between the second pad 46 and attachment pad 42 to prevent from being applied to the signal shorts of LED 34.
With reference to Fig. 8 C and Fig. 8 D, the signal of telecommunication can be by installing pad 50 and second surface is installed pad and 52 be provided external electrical contact to be applied to packaging 30 for the first touch pad 44 and the second touch pad 46 through first surface, and first surface installs pad 50 and second surface is installed pad 52 and is formed on the back sides 54 of time adhesion base station 32 to be directed at least in part with the first touch pad 44 and the second touch pad 46 respectively.The secondary adhesion base station 32 that conductive path 56 is passed through between the first installation pad 50 and the first touch pad 44 is formed so that the signal being applied to the first installation pad 50 is transmitted to the first touch pad 44.Similarly, conductive path 56 is installed second and is formed so that the signal of telecommunication conducts between pad 52 and the second touch pad 46.First installation pad 50 and second installs pad 50 permission surfaces installation LED packaging 30, LED to be applied to The signal of telecommunication of 34 is installed pad 50 and second first and is installed application on pad 52.
The thermally conductive pathways that pad 42,44,46 offer extends is warm away from LED 34 with conduction.Attachment pad 42 covers the surface of the secondary adhesion base station 32 bigger than LED 34, and wherein this attachment pad extends from the edge of LED 34 to the edge of secondary adhesion base station 32.Touch pad 44,46 also covers time adhesion base station 32 surface between the edge of path 56 and secondary adhesion base station 32.By extending pad 42,44,46, can improve the heat distribution from LED 34, this can improve the operation lifetime of LED and/or allow higher operating power.
LED packaging 30 is additionally included on the back side 54 of time adhesion base station 32 installs the metallized area 66 between pad 50 and the second installation pad 52 first.Metallized area 66 can be made from a material that be thermally conductive and can be with LED 34 perpendicular alignmnet at least in part.In some embodiments, metallized area 66 does not installs pad 52 electrical contact with the element on the end face of secondary adhesion base station 32 or the first installation pad 50 and second on the back side of secondary adhesion base station 32.Although the heat from LED is spread on the end face 40 of secondary adhesion base station 32 by attachment pad 42 and pad 44,46, but more heat will be passed directly under secondary adhesion base station 32 and around LED 34.The metallized area 66 that metallized area 66 wherein can more easily can dissipate by allowing this heat to spread to helps this dissipation.This heat also can be conducted through path 56 from the end face 40 of secondary adhesion base station 32, and wherein spreadable the first installation pad 50 and second to the heat that the most also can dissipate of this heat is installed in pad 52.
Should be appreciated that Fig. 8 A-8D shows the LED of a kind of exemplary packaging that can comprise the fluorescencer composition according to embodiment of the present invention.The LED of exemplary packaging additionally is disclosed in the U.S. Provisional Patent Application 61/173,550 that on April 28th, 1 submits to, and the full content of this patent application is incorporated herein in by way of reference, general just as its full text of statement.It is equally understood that the LED structure can packed with any other according to the fluorescencer composition of embodiment of the present invention is used together.
As it has been described above, in some embodiments, can be coated directly onto on the surface of semiconductor crystal wafer before wafer is divided into single led chip according to the fluorescencer composition of embodiment of the present invention.To discuss a kind of method using this fluorescencer composition for Fig. 9 A-9E now.In the example of Fig. 9 A-9E, fluorescencer composition is applied in multiple LED chip 110.In this embodiment, each LED chip 110 is to have the vertical stratification gasifying device of top contact 124 and bottom contact 122.
With reference to Fig. 9 A, multiple LED chip 110 (illustrate only two) represent (that is, before wafer separate/be divided into single led chip) with the wafer scale of its manufacturing process.Each LED chip 110 is included on base material 120 semiconductor LED formed.Each LED chip 110 has the first contact 122 and the second wafer 124.First contact 122 is in the bottom of base material 120, and the second wafer 124 is at the top of LED chip 110.In this specific embodiment, top contact 124 is p-type contact and the contact 122 in the bottom of base material 120 is n-type contact.It will be appreciated, however, that in other embodiments, contact 122,124 can be arranged differently.Such as, in some embodiments, may be formed at both contact 122 and contact 124 on the upper surface of LED chip 110.
As shown in figures 9 b and 9, conductive contact base 128 is formed on top contact 124, and it is made and the electrical contact of p-type contact 124 after being coated with fluorescencer composition in LED chip 110.Base 128 can be formed by many different conductive materials and can use known physics that the many of such as plating, masked-deposition (electron beam, sputtering), electroless-plating or column-shaped projection (stud bumping) is different or chemical deposition to be formed.The height of base 128 can change according to the wanted thickness of fluorescencer composition and should sufficiently high extend from the end face of the fluorescencer composition coating of LED or on the end face of this fluorescencer composition coating with coupling.
As shown in Fig. 9 C, wafer is covered by the fluorescencer composition coating 132 of each covered in LED chip 110, contact 122 and base 128.Fluorescencer composition coating 132 can comprise binding agent and the fluorescencer composition according to one embodiment of the invention.Material for described binding agent can be stable after hardening and the material of substantially transparent, such as polysiloxanes, epoxy resin, glass, unorganic glass, spin glass, electrolyte, BCB, polyamide, polymer etc. in visible wavelength spectrum.Fluorescencer composition coating 132 can use the distinct methods of such as spin coating, distribution, electrophoretic deposition, electrostatic precipitation, printing, jet printing or silk screen printing to apply.Another suitable coating technique is disclosed in the U.S. Patent application 12/717,048 that on March 3rd, 2010 submits to, and the content of this patent application is incorporated herein in by way of reference.Fluorescencer composition coating 132 may then use that suitable curing (such as, heating, ultraviolet (UV), infrared (IR) or air curing) solidifies.
Different factor determines the amount of the LED light absorbed by the fluorescencer composition coating 132 in final LED chip 110, and described factor includes but not limited to the size of fluorophor particle, the percent of fluorophor load capacity, the type of adhesive material, matching efficiency between fluorophor type and wavelength of transmitted light and the thickness of fluorescencer composition coating 132.It should be understood that other fluorophor many can individually or export to be applied in combination to obtain desired combination spectrum.
Various sizes of fluorophor particle can be used, include but not limited to the particle particle to the particle or bigger of 20-30 μ m in size of 10-100 nanometer (nm) size.Compared with the particle of large-size, less particle size generally better scatters and blend color, to provide light evenly.Compared with less particle, bigger particle is generally more effective in terms of conversion light, but launches less uniform light.In some embodiments, described fluorophor particle can be in the size range of about 1 micron-about 30 microns, and wherein the particle of about half is between about 4 microns-about 20 microns.In some embodiments, at least half of fluorophor particle can have the size (diameter) in 2 micron of-20 micrometer range.The most various sizes of fluorophor can be included in fluorescencer composition coating 132 as required, so that end coating 132 can have the reduced size of effectively scattering mixed light and combining of effective large-size changing light.
Coating 132 also can have variable concentrations or the fluorescent material of load capacity in binding agent, and wherein typical concentration is in the range of 30-70 weight %.In one embodiment, described phosphor concentration is about 65 weight %, and generally can be uniformly dispersed in whole binding agent.In other embodiments, coating 132 can include multiple layers of the fluorophor of variable concentrations or type, and the plurality of layer can comprise different adhesive materials.One or more in these layers can provide in the case of not having fluorophor.Such as, the first coating of clarification polysiloxanes can be deposited, be followed by loading the layer of fluorophor.As another example, described coating can include the ground floor with a type of fluorophor being such as included in LED chip 110 and the duplex coating of the second layer the most on the first layer of the fluorophor comprising Second Type.May have other layer structures many, including multilamellar, described multilamellar comprises multiple fluorophor within the same layer, and between the layers and/or between coating and bottom LED chip 110, may also provide interposed layer or element.
After by fluorescencer composition coating 132 initial coat LED chip 110, it is necessary to be processed further exposing base 128.With reference now to Fig. 9 D, coating 132 thinning or planarization are exposed base 128 with the end face via coating 132.This thinning technique exposes base 128, makes coating 132 planarize and allow to control the final thickness of coating 132.Based on the LED 110 operating characteristic on wafer and the character of selected fluorophor (fluorescence) material, the final thickness of coating 132 can be calculated to realize desired color dot/scope and still to expose base 128.The thickness of coating 132 can be uniformly or non-uniformly on wafer.Any suitable coating layer thickness can be used.But, in some embodiments, described coating is less than 1mm, and in some embodiments, described coating is less than 500 μm, and in some embodiments, described coating is less than 100 μm, and in some embodiments, described coating is less than 10 μm.
As shown in fig. 9e, after using coating 132, single led chip 110 can use the known method of such as cutting, scribing and disconnection or etching to split from wafer.This division process separates each LED chip 110, and it each has the thickness of essentially identical coating 132 and therefore has the fluorophor of essentially identical amount and therefore have essentially identical emission characteristics.After segmentation LED chip 110, the layer of coating 132 is retained on the side of LED 110 and from the light of the side-emitted of LED 110 also through coating 132 and fluorophor particle thereof.This causes at least some side-emitted light to change, and it may be provided in the LED chip 110 in different viewing angle with the more consistent characteristics of luminescence.
Upon splitting, LED chip 110 can be arranged in packaging or is installed on time adhesion base station or printed circuit board (PCB) (PCB), without being processed further adding fluorophor.In one embodiment, described packaging/time adhesion base station/PCB can have conventional packaging wire, and wherein base 128 is electrically connected to described wire.Therefore can encapsulate around LED chip 110 is conventional and electrically connect.
Although above-mentioned coating process provides a kind of illustrative methods manufacturing the solid luminous device according to embodiment of the present invention including LED and fluorescencer composition, it is to be understood that other manufacture methods various can be used.Such as, the U.S. Patent application 11/899,790 (U.S. Patent Application Publication 2008/0179611) (entire contents is incorporated herein in the most by way of reference) of JIUYUE in 2007 submission on the 7th discloses the various other method of fluorescencer composition coatings to solid luminous device.In other embodiments, light-emitting device LED chip can be arranged on transmitting cup by means of welding compound bonding or conductive epoxy resin, and fluorescencer composition can comprise such as fluorophor and be suspended in the sealant material of polysiloxanes therein.This fluorescencer composition can such as be used for partially or even wholly filling described reflector.Therefore, described fluorophor can on described LED or away from and be optically coupled to described LED.
Although should be understood that and describing the present invention already in connection with the LED with vertical geometry, but its LED being equally applicable to there are other geometries, such as there is on the homonymy of LED chip the lateral LED of two contacts.
Many different embodiments are disclosed with accompanying drawing herein in conjunction with description above.Should be understood that and word for word describe and illustrate that each combination of these embodiments and sub-portfolio are incited somebody to action the most loaded down with trivial details and make it obscure.Therefore, this specification (including accompanying drawing) should be construed as the embodiment described herein and complete and use its all combinations of ways and means and the complete written description of sub-portfolio, and should support any this kind of combination or the requirement of sub-portfolio.
Although relate generally to above include that the solid luminous device of LED discusses embodiment of the present invention, it is to be understood that according to a further embodiment of the present invention, it is possible to provide include laser diode and/or other solid-state lighting devices of fluorescencer composition discussed above.It is therefore to be understood that embodiment of the present invention are not limited to LED, but other solid-state lighting devices of such as laser diode can be included.
In the accompanying drawings and the description, have been disclosed for embodiment of the present invention, although and have employed proprietary term, but they are only to use rather than for the purpose limited with general and describing significance, the scope of the present invention is stated in the claims book.

Claims (40)

1. fluorescencer composition, it comprises Ca1-x-ySrxEuyAlSiN3, wherein in the range of 0.50-0.99 and y is less than 0.013 for x, and wherein said fluorescencer composition comprises the silicon aluminum oxynitride of at least 1 weight %.
2. the fluorescencer composition of claim 1, wherein said silicon aluminum oxynitride comprises Si2Al4O4N4。
3. the fluorescencer composition of claim 1, wherein said fluorescencer composition absorb the light under wavelength in the range of 350-530nm and be transmitted in 620-660nm in the range of wavelength under crest frequency.
4. the fluorescencer composition of claim 1, wherein x in the range of 0.50-0.90 and y 0.001 in the range of less than 0.013.
5. the fluorescencer composition of claim 1, wherein in described fluorescencer composition the ratio of Sr Yu Eu in the range of 25-300.
6. the fluorescencer composition of claim 1, wherein said fluorescencer composition exists in granular form and the granule of at least 95% is elongated.
7. fluorescencer composition, it comprises Ca1-x-ySrxEuyAlSiN3, wherein in the range of 0.71-0.99 and y is in the range of 0.001-0.025 for x, and wherein said fluorescencer composition comprises the silicon aluminum oxynitride of at least 1 weight %.
8. the fluorescencer composition of claim 7, wherein said silicon aluminum oxynitride includes Si2Al4O4N4。
9. the fluorescencer composition of claim 7, wherein y is in the range of 0.001-0.013.
10. the fluorescencer composition of claim 7, wherein in described fluorescencer composition the ratio of Sr Yu Eu in the range of 25-300.
The fluorescencer composition of 11. claim 7, wherein said fluorescencer composition exists in granular form and the granule of at least 95% is elongated.
12. light-emitting devices, comprising:
Solid state light emitter；With
Fluorescent coating in solid state light emitter, described fluorescent coating comprises binding agent and fluorescencer composition, and this fluorescencer composition comprises Ca1-x-ySrxEuyAlSiN3Wherein in the range of 0.50-0.99 and y is less than 0.013 for x, wherein said fluorescencer composition concentration present in the fluorescent coating is 30-70 weight %, and wherein said light-emitting device has the CRI value more than 90, and wherein said fluorescencer composition comprises the silicon aluminum oxynitride of at least 1 weight %.
The light-emitting device of 13. claim 12, wherein said solid state light emitter launches the warm white of the correlated color temperature having between 2700K-5400K.
The light-emitting device of 14. claim 12, wherein in described fluorescencer composition the ratio of Sr Yu Eu in the range of 25-300.
The light-emitting device of 15. claim 12, wherein said fluorescencer composition exists in granular form and the granule of at least 95% is elongated.
The light-emitting device of 16. claim 12, wherein said fluorescencer composition exists as the granule of the particle mean size having in 4 μm-20 μ m.
The light-emitting device of 17. claim 12, wherein said fluorescencer composition exists as monocrystalline.
The light-emitting device of 18. claim 12, it also comprises green and/or yellow fluorophor.
19. light-emitting devices, comprising:
Solid state light emitter；With
Comprise Ca1-x-ySrxEuyAlSiN3Fluorescencer composition, wherein in the range of 0.71-0.99 and y is in the range of 0.001-0.025 for x, and wherein said fluorescencer composition comprises the silicon aluminum oxynitride of at least 1 weight %.
The light-emitting device of 20. claim 19, wherein said solid state light emitter launches the warm white of the correlated color temperature having between 2700K-5400K.
The light-emitting device of 21. claim 19, wherein said light-emitting device has the CRI value more than 90.
The light-emitting device of 22. claim 19, wherein in described fluorescencer composition the ratio of Sr Yu Eu in the range of 25-300.
The light-emitting device of 23. claim 19, wherein said fluorescencer composition exists in granular form and the granule of at least 95% is elongated.
The light-emitting device of 24. claim 19, wherein said fluorescencer composition exists as the granule of the particle mean size having in 4 μm-20 μ m.
The light-emitting device of 25. claim 19, it also comprises green and/or yellow fluorophor.
26. methods forming fluorescencer composition, described method includes
The nitride of calcium mixture, strontium, aluminum and silicon and europium source component to form precursor mixture,
In fire-clay crucible, in the case of there is formation gas, described precursor mixture is heated to the temperature in the range of 1500-1800 DEG C,
Ca is comprised to generate1-x-ySrxEuyAlSiN3Fluorescencer composition, wherein in the range of 0.50-0.99 and y is less than 0.013 for x,
Wherein said fluorescencer composition also comprises the silicon aluminum oxynitride phase of at least 1%.
The method of 27. claim 26, wherein said precursor mixture heats in the case of being substantially not present water and oxygen.
The method of 28. claim 26, wherein said silicon aluminum oxynitride includes Si2Al4O4N4。
The method of 29. claim 26, wherein said fire-clay crucible is the most inert in the case of there is described formation admixture of gas.
The method of 30. claim 26, flows around described fire-clay crucible to wherein said formation gas-dynamic.
The method of 31. claim 26, wherein said precursor mixture heats at least 0.5 hour at the first temperature, is heated to the second temperature and lasts at least 0.5 hour and be subsequently heated to the 3rd temperature and last at least 0.5 hour.
The method of 32. claim 31, wherein said first temperature is 800 DEG C, and described second temperature is 1200 DEG C and described 3rd temperature is 1800 DEG C.
The method of 33. claim 26, wherein said fluorescencer composition absorb the light under wavelength in the range of 350-530nm and be transmitted in 620-660nm in the range of wavelength under crest frequency.
The method of 34. claim 26, wherein said fluorescencer composition exists in granular form and the granule of at least 95% is elongated.
35. methods forming fluorescencer composition, described method includes
The nitride of calcium mixture, strontium, aluminum and silicon and europium source component to form precursor mixture,
In fire-clay crucible, in the case of there is formation gas, described precursor mixture is heated to the temperature in the range of 1500-1800 DEG C,
Ca is comprised to generate1-x-ySrxEuyAlSiN3Fluorescencer composition, wherein in the range of 0.71-0.99 and y is in the range of 0.001-0.025 for x,
Wherein said fluorescencer composition also comprises the silicon aluminum oxynitride phase of at least 1%.
36. fluorescencer compositions, it comprises Ca1-x-ySrxEuyAlSiN3Phosphor particle, wherein x < 1 and y < 1, and described Ca1-x-ySrxEuyAlSiN3At least some in phosphor particle is elongated.
The fluorescencer composition of 37. claim 36, wherein 50% or more described Ca1-x-ySrxEuyAlSiN3Phosphor particle is elongated.
The fluorescencer composition of 38. claim 36, wherein 75% or more described Ca1-x-ySrxEuyAlSiN3Phosphor particle is elongated.
The fluorescencer composition of 39. claim 36, wherein 95% or more described Ca1-x-ySrxEuyAlSiN3Phosphor particle is elongated.
The fluorescencer composition of 40. claim 36, wherein in the range of 0.5-0.99 and y is in the range of 0.001-0.025 for x.
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